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Article

Pivotal Role of the Granularity Uniformity of the WO3 Film Electrode upon the Cyclic Stability during Cation Insertion/Extraction

by
Zhaocheng Zhang
1,
Haoyuan Chen
1,
Zicong Lin
1,
Xiongcong Guan
1,
Jiong Zhang
2,
Xiufeng Tang
1,3,*,
Yunfeng Zhan
1,3 and
Jianyi Luo
1,3,*
1
School of Applied Physics and Materials, Wuyi University, Jiangmen 529020, China
2
School of Civil Engineering and Architecture, Wuyi University, Jiangmen 529020, China
3
Research Center of Flexible Sensing Materials and Device Application Technology, Wuyi University, Jiangmen 529020, China
*
Authors to whom correspondence should be addressed.
Nanomaterials 2023, 13(6), 973; https://doi.org/10.3390/nano13060973
Submission received: 10 February 2023 / Revised: 27 February 2023 / Accepted: 28 February 2023 / Published: 8 March 2023
Browse Figures
Review Reports Versions Notes

Abstract

:
Delicate design and precise manipulation of electrode morphology has always been crucial in electrochemistry. Generally, porous morphology has been preferred due to the fast kinetic transport characteristics of cations. Nevertheless, more refined design details such as the granularity uniformity that usually goes along with the porosity regulation of film electrodes should be taken into consideration, especially in long-term cation insertion and extraction. Here, inorganic electrochromism as a special member of the electrochemical family and WO3 films as the most mature electrochromic electrode material were chosen as the research background. Two kinds of WO3 films were prepared by magnetron sputtering, one with a relatively loose morphology accompanied by nonuniform granularity and one with a compact morphology along with uniform particle size distribution, respectively. Electrochemical performances and cyclic stability of the two film electrodes were then traced and systematically compared. In the beginning, except for faster kinetic transport characters of the 50 W-deposited WO3 film, the two electrodes showed equivalent optical and electrochemical performances. However, after 5000 CV cycles, the 50 W-deposited WO3 film electrode cracked seriously. Strong stress distribution centered among boundaries of the nonuniform particle clusters together with the weak bonding among particles induced the mechanical damage. This discovery provides a more solid background for further delicate film electrode design.

1. Introduction

Discovery of cations transporting and accumulating in solid electrodes (i.e., establishment of the intercalation theory [1]) has greatly propelled electrochemical technology, making spurts of progress. High-performance ion batteries [2], metal batteries [3], supercapacitors [4], and many other electrochemical devices [5] are constantly emerging. Inorganic electrochromism, as a special member of the electrochemical family, combines sustainable, reversible color changes for certain electroactive materials with cation insertion and extraction process upon the application of an electrical voltage [6]. Being capable of dynamically modulating heat and light on demand, electrochromic (EC) technology is highly expected as a promising solution for energy conservation and life-quality improvement, and it has captured much attention for decades [7,8,9]. With broader and broader applications in light adjustment [10], displays [11], electronic devices, and many others [12,13,14], two developing trends have formed in EC technology. On one hand, in academia, all-solid-state, more colorful, more functional, and faster-responding high-performance EC materials and technologies have been consistently advancing [15,16,17]. On the other hand, in the industrializing process, better stability, lower costs, and composite electrolyte and monolithic device optimization were explored [18,19,20].
WO3 EC films are most mature in application, originating from large optical modulation, low cost, great cyclic stability, as well as facile synthesis [8], and numerous efforts have been made to further improve their performances through doping [21], compounding with Nb2O5 or V2O5 [22,23], and other ways [24]. Undoubtedly, cyclic stability is the most decisive factor in real use. For WO3 films, the cyclic failure is generally attributed to the following two aspects: (1) electrochemical failure due to irreversible injection and massive accumulation of Li ions in the film [25]; and (2) volume expansion during cation injection/extraction, resulting in mechanical cracking of the film [26]. Either way, improving cyclic stability requires delicate design of the film electrode, where morphology of the WO3 film is the most important both for the electrochemical performances and the cyclic stability, which has been continuously optimized through modulating the heat-treatment temperature [27], the annealing method [28], preparation parameters [29,30], the crystallization, and nanostructures [31,32]. As a matter of fact, in the whole electrochemical field, morphology design and regulation has always been the primary way to improve electrode performances and the cyclic stability [33,34,35]. The common standing is that electrodes with high porosity or extensive grain boundaries are preferred, as they support rapid cation insertion/extraction [28,36]. However, optimization of the electrode morphology should be comprehensively balanced between the electrochemical characters and the cyclic stability. In addition, facing more sophisticated and harsh demands on electrochemical devices, more elaborate details urgently need to be taken into consideration during electrode designs, such as the granularity uniformity that usually goes along with porosity regulating of the film electrode.
Herein, the WO3 film electrode and the EC technology were taken as the research background where the WO3 films were prepared by magnetron sputtering. Instead of sputtering pressure or ratios of Ar/O2, both of which could significantly regulate the film morphology [29,30], sputtering power was selected to minutely regulate the WO3 film morphology [31] and we depicted how such minute changes of the film morphology could play a pivotal role on the cyclic stability during cations’ insertion/extraction.

2. Experimental Section

2.1. Preparation of the Functional Films

Indium tin oxide (ITO)-coated glass substrates (1.1 mm thickness, ∼6 Ω sheet resistance) were purchased from Zhuhai Kaivo Optoelectronic Technology Co., Ltd. (Zhuhai, China), which were successively subjected to cleaning by acetone, alcohol, and deionized water before use. WO3 films were fabricated by direct current (DC) reactive magnetron sputtering using the JCP-500 sputtering system (Technol.cn) using a tungsten target with purity of 99.999%, 3 mm in thickness, and 3 inches in diameter. The target substrate separation was 110 mm. The background pressure was 6.0 × 10−4 Pa, and the working pressure was 1.4 Pa with an Ar flow rate of 16 sccm and an O2 flow rate of 6 sccm. The sputtering power was selected to tune the film morphology, which was set as 50 W, 80 W, 100 W, and 120 W. The substrate temperature was 25 °C. The deposition duration was 0.36~2.7 h to keep the film thickness constant. Meanwhile, the 1 mol L−1 Li ion electrolyte was prepared by dissolving LiClO4 in polycarbonate (PC) solution.

2.2. Characterization and Performance Tests

The film thickness was tested by a step profiler (Dektak XT Bruker), and all the prepared WO3 films were about 450 nm in thickness. Crystallization of the WO3 film was examined by X-ray diffraction (XRD) analysis using Cu Kα radiation (Philips X’Pert diffractometer). Surface and cross-sectional morphologies of the WO3 film were studied by scanning electron microscopy (SEM) using a Sigma 500 instrument (Zeiss). Tapping-mode atomic force microscopy (AFM) was performed using a Bruker Dimension Fast Scan to in situ monitor the morphology variation of the WO3 film during insertion and extraction of Li ions in the first EC cycle. Transmittance spectra were recorded using a UV−vis spectrophotometer (Shimadzu uv 3150, Japan). The cyclic stability was recorded by cyclic voltammetry (CV); the response time was measured by chronoamperometry measurement (CA), and diffusion coefficients of lithium ions in the WO3 films were analyzed from the (CV) characteristics at different scan rates. Adhesion between the WO3 film and the ITO glass substrate was tested by adhesive tape method, and the testing process was divided into three steps. First, transmittance of the WO3 film at 550 nm in the initial state (T0) was measured by UV/Vis spectrophotometer. Second, the ScotchTM adhesive tape at the force of 4.7 N/cm was leveled and tightly attached to the surface of the WO3 film. Then, the tape was torn up, and transmittance of the WO3 film at 550 nm was measured again (Tn). The adhesion factor f was calculated according to the equation f = 1 − (Tn − T0)/(100 − T0). The closer the value of f was to 1, the greater the adhesion of the WO3 film was because at this time, almost no film was attached to the adhesive tape. On the contrary, the closer the value of f got to 0, the worse the adhesion of the WO3 film was. At this moment, the whole film was almost adhered to the adhesive tape. Finally, stress distribution in the WO3 film during Li ions’ insertion and extraction was analyzed by finite element simulation using the software package ABAQUS.

3. Results and Discussion

With the sputtering power ranging from 50 W to 120 W, the prepared WO3 films were all amorphous, which is preferred in application for the fast response and satisfactory coloration efficiency [31] (corresponding XRD spectra shown in Figure S1). Meanwhile, the surface morphology of the WO3 films showed minute but regular changes (Figure 1 and Figure S2). When the sputtering power was as low as 50 W (Figure 1a), relatively loose morphology was shown, containing both large, agglomerated clusters and fine particles, and the particle size centered at 28 nm with a wide range of 12.5~42.5 nm. For 80 W (Figure S2b), the film became compact and was composed of nonuniform clusters, some parts with super-fine particles and others with big ones, and the particle size centered at 20 nm and 26 nm with a relatively narrow range of 14~38 nm. Up to 100 W (Figure 1b), the film seemed uniform and compact, and the particle size mostly centered between 14 nm and 17.5 nm with the narrowest range of 12~23 nm. When the sputtering power was further increased to 120 W, the film morphology turned back to the large, agglomerated morphology (Figure S2d), along with a broad particle size distribution of 8~32 nm. According to the film growth mechanism, the higher the sputtering power, the bigger the kinetic energy and migrating capability of sputtered particles onto the substrate. Appropriate kinetic energy and migrating capability generally brings about uniform particle size and distribution; too much or too little would both result into particle aggregation and nonuniform granularity. Furthermore, cross-sectional SEM morphology also verified the relatively loose microstructure with nonuniform particle size distribution in the 50 W-deposited WO3 film and the dense packing morphology with uniform granularity in the 100 W-deposited film (Figure S3). Herein, the 50 W-deposited WO3 film and the 100 W-deposited WO3 film were selected, and their electrochemical behaviors and cyclic performances during cation insertion and extraction were recorded and systematically compared to unveil the intrinsic relationship among the porosity and granularity uniformity of the film electrode morphology, its electrochemical characteristics, and its cyclic stability.
As shown in Figure 2, response times of the two films at voltages of ±0.8 V for 20 s were measured by chronoamperometry, where the response time was taken as 90% of the current change [37]. The coloring and bleaching response times of the 50 W-deposited WO3 film were respectively 7.21 s and 2.51 s (Figure 2ai), while those of the 100 W-deposited film were 11.8 s and 5.26 s (Figure 2bi). This indicated that the 50 W-deposited film showed a faster response speed, originating from its relatively loose microstructure (Figure 1a) and enhanced transport dynamics of cations [32]. Moreover, the peak currents of the 50 W-deposited WO3 film during the coloring and bleaching processes were 10.3 mA and 26.8 mA, both higher than those of the 100 W-deposited film at 5.7 mA and 18.4 mA, verifying that lower charge transfer impedance was achieved, and Li ions’ insertion/extraction was facilitated when the film electrode was in relatively loose morphology.
After Li ions’ insertion and the WO3 film being fully colored, memory effects, i.e., the cation retention capability of the film electrodes, were recorded (Figure 2aii,bii). When the films were as-colored, transmittance modulation rates at the wavelength of 550 nm were 73% (from 78.3% to 5.3%) for the 50 W-deposited WO3 film and 76% (from 77.8% to 2.1%) for the 100 W-deposited film. After being exposed in the air for 24 h, the transmittance modulation rate decreased by 26% (from 73% to 47%) for the 50 W-deposited film and 21% (from 76% to 55%) for the 100 W-deposited film. Thus, a better cation retention capability would be achieved for the compact WO3 film, but optical performances of the two films were overall equivalent. In addition, in adhesive force tests with the ITO substrates, the two films also performed fairly, and the adhesion factors f were both 1, meaning excellent adhesive situations between the WO3 films and the ITO substrates were achieved from the magnetron sputtering method, which inherently provides good adhesion with substrates (Figure S4).
The electrochemical cyclic performances of the two WO3 films were analyzed based on their CV curves, shown in Figure 3. From Figure 3ai,bi and Figure S5 (transmittance spectra evolution of the WO3 films during 5000 CV cycles), it could be seen that the transmittance modulation rate at 550 nm monotonically decreased from 73% to 37% after 5000 CV cycles for the 50 W-deposited film. Meanwhile, for the 100 W-deposited film, its transmittance modulation rate showed two sharp decreases during the first 2000 cycles, reducing from 76% to 69% during the first 1000 cycles and then to 61% during the second 1000 cycles, and then slightly declining to 58% in the following 3000 cycles, showing a better optical cyclic stability.
Charge density (mC·cm−2) can be obtained by integrating the CV curves (Figure S6) through Equation (1), where J, V, and s are the current density (mA·cm−2), voltage (V), and scanning rate (V·s−1), respectively.
C = ∫ J d V s
The calculated charge capacities of inserted (Qin), extracted (Qex), and trapped (Qex/Qin) Li ions vs. the cycle number are shown in Figure 3aii,bii. In the beginning, the charge capabilities of the two films were both 2.88 mC·cm−2. For the 50 W-deposited film, it monotonically decreased to 1.04 mC·cm−2 after 5000 CV cycles, and the attenuation rate was calculated to be 64%; while for the 100 W-deposited WO3 film, the charge capacity decreased stage by stage, sharp declining from 2.73 mC·cm−2 to 1.72 mC·cm−2 during the second 1000 cycles, reaching a platform stage from the 2000th cycle to 3000th cycle, and then sharply declining to 1.18 mC·cm−2 in the last 2000 cycles. The attenuation rate was calculated as 59%, behaving slightly better than the 50 W-deposited film. It should be noted that during the 5000 CV cycles, variation trends of the optical modulation rate and the charge capacity of the two films were consistent.
However, as for the trapping and accumulation of Li ions in the films denoted by Qex/Qin, for the 50 W-deposited WO3 film, Qex/Qin decreased from 69% to 66% at a very slow rate during the first 4000 cycles and then sharply declined to 55% during the last 1000 cycles, meaning that more Li ions were trapped at this time. Meanwhile, for the 100 W-deposited WO3 film, Qex/Qin decreased from 66% to 63% at a very slow rate during the first 3000 cycles, then sharply declined to 54% after 4000 cycles, and kept decreasing to 48% during the last 1000 cycles, which means much more Li ions were trapped in the 100 W-deposited film than the 50 W-deposited sample during the 5000 CV cycles because of its compact microstructure.
Furthermore, diffusion coefficients of Li ions (D) during the coloring and bleaching processes were analyzed according to the Randles–Servcik Equation (Equation (2)) from the CV characteristics at different scan rates v, illustrated in Figure 3aiii,biii (the original CV curves are shown in Figures S7 and S8, and analyzed evolutions of the redox peaks versus square root of the scanning rate are shown in Figure S9) [38].
D 1 / 2 = i P c / P a 2.69 × 10 5 × A × C 0 × n 3 / 2 × v 1 / 2
where iPc and iPa are the oxidation and reduction peak current intensities, A/cm2; A the effective area of electrochromic film, cm2; v is the scanning rate, V/s; C0 is the concentration of the cations in electrolyte, mol/cm3; and n is the number of involved electrons.
In the as-deposited state, the Li ions’ diffusion coefficient of the 50 W-deposited WO3 film were respectively 13.34 × 10−10 and 11.05 × 10−10 cm2/s in the coloring and bleaching process, which were slightly higher than those of the 100 W-deposited film of 12.89 × 10−10 and 10.7 × 10−10 cm2/s. This suggested that the faster response time of the 50 W-deposited film was probably because the interfacial transport of Li ions was facilitated rather than the bulk diffusion process, when the film was gifted a relatively loose morphology. During the 5000 CV cycles, diffusion coefficients both monotonously decreased for the two films because the more and more trapped Li ions would block the transport pathways in the film. However, the diffusion coefficients of the 50 W-deposited film slowly declined to 9.4 × 10−10 cm2/s during the coloring process and 5.61 × 10−10 cm2/s during the bleaching process; while for the 100 W-deposited film, they respectively decreased sharply to 4.4 × 10−10 cm2/s and 2.8 × 10−10 cm2/s after 5000 CV cycles, which suggested that morphology of the two films inevitably changed during such long-term Li ion insertion and extraction.
Thus, the surface morphology of the two film electrodes during the 5000 CV cycles were recorded and are shown in Figure 4. Overall, for both films, particles got finer and finer, which could also be responsible for the decreasing diffusion coefficients. However, the 50 W-deposited WO3 film finally cracked where the cluster profiles kept unchanged but the component particles had become finer during the first three cycles; after 1000 cycles, the component particles became even finer and the clusters seemed to be flattened with clearly seen borders filled with pores; after 3000 cycles, the film became nonuniform and was composed of relatively loose clusters mingled with some compact areas and several micro-cracks; after 5000 cycles, the film became very smooth and compact, and no particles and cluster profiles could be seen except huge cracks (Figure 4a). The morphology evolution could reasonably explain why Qex/Qin dropped sharply during the last 1000 cycles for the 50 W-deposited film (Figure 3aii). For the 100 W-deposited WO3 film (Figure 4b), similar variations happened to the morphology during the first three cycles; after 1000 cycles, cluster profiles blurred and the whole morphology was composed of a main compact area and some loose areas; while after 3000 cycles, the film returned to uniform and compact, and no more cluster profiles could be seen; after 5000 cycles, it still remained compact and uniform, and no mechanical damages were shown.
The morphology variation during the insertion and extraction of Li ions was recorded by in situ AFM (Figure 5), from which obvious different behaviors were observed for the two films. In the as-deposited state, particle cluster spikes could be seen on both surfaces of the two films, and their surface roughness values were similar at 8.09 nm for the 50 W-deposited film and 8.20 nm for the 100 W-deposited film. Once colored, the surface roughness values both decreased to 3.30 nm and 4.44 nm, respectively. However, for the particle cluster spikes, remarkable differences were observed in the two films. For the 50 W-deposited film (Figure 5aii), those cluster spikes became fat and were surrounded by gully regions. Once the Li ions started being extracted
(Figure 5aiii), although most of the cluster spikes returned to their as-deposited states with the surface roughness increasing to 6.20 nm, the film surface seemed full of bumps and gullies, even more rough than its as-deposited state. Contrarily, for the 100 W-deposited WO3 film, when Li ions were inserted (Figure 5bii), most cluster spikes disappeared, but some new small spikes appeared and dispersed well on the film surface. With Li ions being extracted (Figure 5biii), almost all spikes disappeared, and the surface roughness further decreased to 4.14 nm. These AFM results of the single process of Li ion insertion and extraction could be regarded a perfect epitome of the evolution of the film surface morphology during the 5000 CV cycles (Figure 4).
Ultimately, to deeply interpret the stress distribution in the WO3 film during cation insertion, finite element simulation was carried out using the software package ABAQUS, where the WO3 film was assumed to be perfectly bonded to a rigid substrate and the substrate was homogeneous and isotropic. Inhomogeneous bodies were employed to simulate the 50 W-deposited WO3 film with nonuniform particle size distribution (Figure 6ai), while the 100 W-deposited WO3 film was simulated as homogeneous and isotropic as the substrate (Figure 6bi). In this simulation, the WO3 film was supposed to be elastic, and the elastic modulus and the elastic properties of the inhomogeneous bodies were assumed to be much less than those of the uniform WO3 film. As can be seen from Figure 6bii, for the uniform 100 W-deposited film, stresses mainly centered in the middle of the film, but the two interface edges withstood a larger stress concentration. In this situation, under long-term cation insertion and extraction, the WO3 film more easily disconnected with the substrate and fell off as a whole. However, due to the nonuniform granularity of the 50 W-deposited film, stresses were much higher and mainly centered among boundaries of the inhomogeneous bodies. Additionally, the two interface edges also withstood a larger stress concentration than that of the uniform 100 W-deposited film. Therefore, under long-term cation insertion and extraction, cracks were more likely to generate in the WO3 film. The above simulation was verified by cross-sectional SEM images of the two WO3 films after 5000 CV cycles, as shown in Figure 6aiii,biii. In contrast with the 100 W-deposited film showing smooth and compact morphology, plenty of fragments and internal cracks were found in the 50 W-deposited WO3 film. It was interesting to note that during sample preparation of the SEM tests, it was hard to obtain smooth cross-sectional morphology for the 50 W-deposited film, and particle fragments always existed in the image both for the as-deposited state (Figure S3a) and the 5000-cycled ones (Figure 6aiii), indicating weak bonding among the particles of the 50 W-deposited film. The strong stress distribution centered among cluster boundaries in combination with the weak bonding among particles were both responsible for its surface morphology variation, where the cluster spikes were surrounded by gullies after Li ion insertion and the cluster borders were filled with pores after 1000 cycles of Li ion insertion and extraction, until the final mechanical damage after 5000 CV cycles (Figure 4a and Figure 5a). However, for the 100 W-deposited film (Figure S3b and Figure 6biii), smooth cross-sectional morphologies were easily obtained, suggesting the strong bonding among particles in the film, which perfectly explained why those cluster spikes were stretched by each other and disappeared during one-step Li ion insertion (Figure 5bii), and those scattered loose areas present in the 1000-cycled film would return to being uniform after 3000 CV cycles (Figure 4b).

4. Conclusions

In this work, the intrinsic relationship among the porosity and granularity uniformity of the film electrode morphology, its electrochemical characteristics, and the cyclic stability were demonstrated. Two kinds of WO3 films, one with a relatively loose morphology accompanied by nonuniform granularity and one with a compact morphology along with uniform particle size distribution were respectively obtained at the sputtering powers of 50 W and 100 W. As expected, owing to its relatively loose morphology, the 50 W-deposited film exhibited faster coloring and bleaching response times of 7.21 s and 2.51 s compared to the 100 W-deposited film, but had a worse capability of cation retention. The adhesive, electrochemical, and optical performances of the two film electrodes were equivalent in the beginning. However, during 5000 CV cycles, the cyclic stability of the 50 W-deposited WO3 film with cracked morphology and high transmittance modulation decay was far behind that of the 100 W-deposited film, though many more Li ions were trapped in the latter, known from its smaller Qex/Qin throughout. The strong stress distribution during Li ion insertion centering among boundaries of the nonuniform clusters and the weak bonding among particles in the relatively loose 50 W-deposited film together induced the final mechanical damage. These results demonstrated that although porosity gifts film electrodes fast kinetic characters, it also brings about weak bonding among active particles and weakens their mechanical cyclic stability during long-term cation insertion and extraction, and the granularity nonuniformity that generates strong local stresses would further aggravate such processes. Our study is an important attempt toward a more delicate design of the film electrode morphology, highlighting the trade-off between the kinetic behavior and the cyclic stability.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/nano13060973/s1, Figure S1: XRD spectra of the prepared WO3 films; Figure S2: SEM images of the prepared WO3 films (i) and corresponding particle size distribution analysis through Nano Measure software (ii), a 50 W; b 80 W; c 100 W; d 120 W, where red-line circles in a and c pictured the particle size distribution; Figure S3: Cross-sectional SEM images of the as-prepared WO3 films, a 50 W; b 100 W, where red-line circles in a pictured the particle size distribution; Figure S4: Adhesive force analysis of the as-prepared WO3 films with ITO substrates; Figure S5: Evolution of transmittance spectra of the WO3 films during 5000 cyclic voltammetry, a 50 W; b 100 W; Figure S6: Evolution of CV curves of the WO3 films during 5000 CV cycles at the scanning rate of 0.1 V/s versus Ag/AgCl, a 50 W; b 100 W; Figure S7: CV curves of the 50W-deposited WO3 film during 5000 CV cycles at scanning rates ranging from 0.01 to 0.1 V/s versus Ag/AgCl, a the first cycle; b the 1000th cycle; c the 2000th; d the 3000th cycle; e the 4000th cycle; f the 5000th cycle; Figure S8: CV curves of the 100W-deposited WO3 film during 5000 CV cycles at scanning rates ranging from 0.01 to 0.1 V/s versus Ag/AgCl, a the first cycle; b the 1000th cycle; c the 2000th cycle; d the 3000th cycle; e the 4000th cycle; f the 5000th cycle.cycle; d the 3000th cycle; e the 4000th cycle; f the 5000th cycle(CV) cycles; Figure S9: Evolution of the redox peaks versus square root of the scanning rate, a in bleaching process of the 50W-deposited film; b in coloring process of the 50W-deposited film; c in bleaching process of the 100W-deposited film; d in coloring process of the 100 W-deposited film.

Author Contributions

Z.Z. and X.T. was responsible for the study design; data analysis; manuscript writing and final revision. J.L. and Y.Z. was responsible for the study design; data analysis; manuscript writing and final revision. H.C. and Z.L. was responsible for data collection, manuscript writing, and final review. X.G. and Y.Z. were responsible for data analysis; manuscript writing and final revision. J.Z. were responsible for data analysis; manuscript writing and final revision. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding. The research was supported by the National Natural Science Foundation of China (No.12004285), the Guangdong Natural Science Foundation of China (No.2021A1515011935), the Guangdong Basic and Applied Basic Research Foundation No.(2019A1515111190), and the Guangdong Innovation and Strengthening School Project Foundation (No.2022ZDZX3033), Guangdong Engineering Technology Research Center (No.2021J020).

Data Availability Statement

Data is unavailable due to the privacy of participants.

Acknowledgments

The major work was carried out at the School of Applied Physics and Materials and Research Center of Flexible Sensing Materials and Devices in Wuyi University. The authors gratefully acknowledge the financial support of the National Natural Science Foundation (No. 12004285), Natural Science Foundation of Guangdong Province (No. 2021A1515011935), Guangdong Basis and Applied Fundamental Research Fund (No. 2019A1515111190), Innovation and Strong School Engineering Fund of Guangdong Province (2022ZDZX3033), Guangdong Engineering Technology Research Center (No. 2021J020).

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Vashishta, P.; Mundy, J.; Shenoy, G. Fast ion transport in solids: Electrodes and electrolytes. Solid State Commun. 1979, 29, 5–6. [Google Scholar]
  2. Ge, J.; Fan, L.; Rao, A.M.; Zhou, J.; Lu, B. Surface-substituted Prussian blue analogue cathode for sustainable potassium-ion batteries. Nat. Sustain. 2021, 5, 225–234. [Google Scholar] [CrossRef]
  3. Xiong, P.; Zhang, F.; Zhang, X.; Liu, Y.; Wu, Y.; Wang, S.; Safaei, J.; Sun, B.; Ma, R.; Liu, Z.; et al. Atomic-scale regulation of anionic and cationic migration in alkali metal batteries. Nat. Commun. 2021, 12, 4184. [Google Scholar] [CrossRef] [PubMed]
  4. Qin, H.; Liu, P.; Chen, C.; Cong, H.; Yu, S. A multi-responsive healable supercapacitor. Nat. Commun. 2021, 12, 4297. [Google Scholar] [CrossRef]
  5. Gu, J.; Liu, S.; Ni, W.; Ren, W.; Haussener, S.; Hu, X. Modulating electric field distribution by alkali cations for CO2 electroreduction in strongly acidic medium. Nat. Catal. 2022, 5, 268–276. [Google Scholar] [CrossRef]
  6. Yao, Y.; Zhao, Q.; Wei, W.; Chen, Z.; Zhu, Y.; Zhang, P.; Zhang, Z.; Gao, Y. WO3 quantum-dots electrochromism. Nano Energy 2020, 68, 104350. [Google Scholar] [CrossRef]
  7. Crandall, R.S.; Faughnan, B.W. Electronic transport in amorphous HxWO3. Phys. Rev. Lett. 1977, 39, 232. [Google Scholar] [CrossRef]
  8. Granqvist, C.G. Electrochromics for smart windows: Oxide-based thin films and devices. Thin Solid Films 2014, 564, 1–38. [Google Scholar] [CrossRef]
  9. Wang, L.; Guo, M.; Zhan, J.; Jiao, X.; Chen, D.; Wang, T. A new design of an electrochromic energy storage device with high capacity, long cycle lifetime and multicolor display. J. Mater. Chem. A 2020, 8, 17098–17105. [Google Scholar] [CrossRef]
  10. Baetens, R.; Jelle, B.P.; Gustavsen, A. Properties, requirements and possibilities of smart windows for dynamic daylight and solar energy control in buildings: A state-of-the-art review. Sol. Energy Mater. Sol. Cells 2010, 94, 87–105. [Google Scholar] [CrossRef] [Green Version]
  11. Zhang, W.; Wang, X.; Wang, Y.; Yang, G.; Gu, C.; Zheng, W.; Zhang, Y.; Li, M.; Zhang, S. Bio-inspired ultra-high energy efficiency bistable electronic billboard and reader. Nat. Commun. 2019, 10, 1559. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  12. Qian, K.; Cai, G.; Nguyen, V.C.; Chen, T.; Lee, P.S. Direct Observation of Conducting Filaments in Tungsten Oxide Based Transparent Resistive Switching Memory. ACS Appl. Mater. Interfaces 2016, 8, 27885–27891. [Google Scholar] [CrossRef]
  13. Xiao, L.; Lv, Y.; Lin, J.; Hu, Y.; Dong, W.; Guo, X.; Fan, Y.; Zhang, N.; Zhao, J.; Wang, Y.; et al. WO3-Based Electrochromic Distributed Bragg Reflector: Toward Electrically Tunable Microcavity Luminescent Device. Adv. Opt. Mater. 2018, 6, 1700791. [Google Scholar] [CrossRef]
  14. Besnardiere, J.; Ma, B.; Torres-Pardo, A.; Wallez, G.; Kabbour, H.; Gonzalez-Calbet, J.M.; Von Bardeleben, H.J.; Fleury, B.; Buissette, V.; Sanchez, C.; et al. Structure and electrochromism of two-dimensional octahedral molecular sieve h’-WO3. Nat. Commun. 2019, 10, 327. [Google Scholar] [CrossRef] [Green Version]
  15. Li, R.; Ma, X.; Li, J.; Cao, J.; Gao, H.; Li, T.; Zhang, X.; Wang, L.; Zhang, Q.; Wang, G.; et al. Flexible and high-performance electrochromic devices enabled by self-assembled 2D TiO2/MXene heterostructures. Nat. Commun. 2021, 12, 1587. [Google Scholar] [CrossRef]
  16. Wang, J.; Zhang, L.; Yu, L.; Jiao, Z.; Xie, H.; Lou, X.; Sun, X. A bi-functional device for self-powered electrochromic window and self-rechargeable transparent battery applications. Nat. Commun. 2014, 5, 4921. [Google Scholar] [CrossRef] [Green Version]
  17. Shao, Z.; Huang, A.; Ming, C.; Bell, J.; Yu, P.; Sun, Y.; Jin, L.; Ma, L.; Luo, H.; Jin, P.; et al. All-solid-state proton-based tandem structures for fast-switching electrochromic devices. Nat. Electron. 2022, 5, 45–52. [Google Scholar] [CrossRef]
  18. Tian, Y.; Zhang, W.; Cong, S.; Zheng, Y.; Geng, F.; Zhao, Z. Unconventional Aluminum Ion Intercalation/Deintercalation for Fast Switching and Highly Stable Electrochromism. Adv. Funct. Mater. 2015, 25, 5833–5839. [Google Scholar] [CrossRef]
  19. Fang, H.; Zheng, P.; Ma, R.; Xu, C.; Yang, G.; Wang, Q.; Wang, H. Multifunctional hydrogel enables extremely simplified electrochromic devices for smart windows and ionic writing boards. Mater. Horiz. 2018, 5, 1000–1007. [Google Scholar] [CrossRef]
  20. Tang, X.; Chen, G.; Li, Z.; Li, H.; Zhang, Z.; Zhang, Q.; Ou, Z.; Li, Y.; Qi, C.; Luo, J. Structure evolution of electrochromic devices from ‘face-to-face’ to ‘shoulder-by-shoulder’. J. Mater. Chem. C 2020, 8, 11042–11051. [Google Scholar] [CrossRef]
  21. Zhan, Y.; Tan, M.; Cheng, X.; Tan, W.; Cai, G.; Chen, J.; Kumar, V.; Magdassi, S.; Lee, P.S. Ti-Doped WO3 synthesized by a facile wet bath method for improved electrochromism. J. Mater. Chem. C 2017, 5, 9995–10000. [Google Scholar] [CrossRef]
  22. Park, Y.J.; Kang, K.M.; Kang, J.H.; Han, S.H.; Jang, H.S.; Lee, J.Y.; Yoon, T.S.; Nah, Y.C.; Kim, D.H. Enhancement of electrochromic response and cyclic durability of WO3 thin films by stacking Nb2O5 layers. Appl. Surf. Sci. 2022, 582, 152431. [Google Scholar] [CrossRef]
  23. Prasad, A.K.; Park, J.Y.; Kang, S.H.; Ahn, K.S. Electrochemically co-deposited WO3-V2O5 composites for electrochromic energy storage applications. Electrochim. Acta 2022, 422, 140340. [Google Scholar] [CrossRef]
  24. Hua, C.; Yuan, G.; Cheng, Z.; Jiang, H.; Xu, G.; Liu, Y.; Han, G. Building architecture of TiO2 nanocrystals embedded in amorphous WO3 films with improved electrochromic properties. Electrochim. Acta 2019, 309, 354–361. [Google Scholar] [CrossRef]
  25. Wen, R.T.; Granqvist, C.G.; Niklasson, G.A. Eliminating degradation and uncovering ion-trapping dynamics in electrochromic WO3 thin films. Nat. Mater. 2015, 14, 996–1001. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  26. Tang, X.; Chen, G.; Liao, H.; Li, Z.; Zhang, J.; Luo, J. Unveiling mechanical degradation for a monolithic electrochromic device: Glass/ITO/WO3/LiClO4 (PEO)/TiO2/ITO/glass. Electrochim. Acta 2020, 329, 135182. [Google Scholar] [CrossRef]
  27. Shinde, P.A.; Lokhande, A.C.; Chodankar, N.R.; Patil, A.M.; Kim, J.H.; Lokhande, C.D. Temperature dependent surface morphological modifications of hexagonal WO3 thin films for high performance supercapacitor application. Electrochim. Acta 2017, 224, 397–404. [Google Scholar] [CrossRef]
  28. Mallikarjuna, K.; Shinde, M.; Kumar, A.; Ryu, J.; Kim, H. Photonic Drying/Annealing: Effect of Oven/Visible Light/Infrared Light/Flash-Lamp Drying/Annealing on WO3 for Electrochromic Smart Windows. ACS Sustain. Chem. Eng. 2021, 9, 14559–14568. [Google Scholar] [CrossRef]
  29. Sun, S.; Tang, C.; Jiang, Y.; Wang, D.; Chang, X.; Lei, Y.; Wang, N.; Zhu, Y. Flexible and rechargeable electrochromic aluminium-ion battery based on tungsten oxide film electrode. Sol. Energy Mater. Sol. Cells 2020, 207, 110332. [Google Scholar] [CrossRef]
  30. Karthik Yadav, P.V.; Ajitha, B.; Reddy, A.K.; Minnam Reddy, V.R.; Reddeppa, M.; Kim, M.D. Effect of sputter pressure on UV photodetector performance of WO3 thin films. Appl. Surf. Sci. 2021, 536, 147947. [Google Scholar] [CrossRef]
  31. Zhao, Y.; Zhang, X.; Li, W.; Li, Z.; Zhang, H.; Chen, M.; Sun, W.; Xiao, Y.; Zhao, J.; Li, Y. High-performance electrochromic WO3 film driven by controllable crystalline structure and its all-solid-state device. Sol. Energy Mater. Sol. Cells 2022, 237, 111564. [Google Scholar] [CrossRef]
  32. Yuan, G.; Hua, C.; Khan, S.; Jiang, S.; Wu, Z.; Liu, Y.; Wang, J.; Song, C.; Han, G. Improved electrochromic performance of WO3 films with size controlled nanorods. Electrochim. Acta 2018, 260, 274–280. [Google Scholar] [CrossRef]
  33. Miller, J.R.; Outlaw, R.A.; Holloway, B.C. Graphene double-layer capacitor with ac line-filtering performance. Science 2010, 329, 1637–1639. [Google Scholar] [CrossRef] [PubMed]
  34. Zheng, J.; Archer, L.A. Controlling electrochemical growth of metallic zinc electrodes: Toward affordable rechargeable energy storage systems. Sci. Adv. 2021, 7, 219. [Google Scholar] [CrossRef]
  35. Li, J.; Sharma, N.; Jiang, Z.; Yang, Y.; Monaco, F.; Xu, Z.; Hou, D.; Ratner, D.; Pianetta, P.; Cloetens, P.; et al. Dynamics of particle network in composite battery cathodes. Science 2022, 376, 517–521. [Google Scholar] [CrossRef]
  36. Deepa, M.; Srivastava, A.K.; Sharma, S.N.; Govind; Shivaprasad, S.M. Microstructural and electrochromic properties of tungsten oxide thin films produced by surfactant mediated electrodeposition. Appl. Surf. Sci. 2008, 254, 2342–2352. [Google Scholar] [CrossRef]
  37. Li, Z.; Liu, Z.; Li, J.; Yan, W. The electrochromic properties of the film enhanced by introducing oxygen vacancies to crystalline tungsten oxide. Colloids Surf. A 2022, 641, 128615. [Google Scholar] [CrossRef]
  38. Guo, J.; Wang, M.; Diao, X.; Zhang, Z.; Dong, G.; Yu, H.; Liu, F.; Wang, H.; Liu, J. Prominent Electrochromism Achieved Using Aluminum Ion Insertion/extraction in Amorphous WO3 Films. J. Phys. Chem. C 2018, 122, 19037–19043. [Google Scholar] [CrossRef]
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Figure 1. SEM images of the as-prepared WO3 films and corresponding particle size distribution analysis through Nano Measure software; (a) 50 W; (b) 100 W, (ai) and (bi) are SEM images, where red line circles in (ai) and (bi) picture the particle size distribution, (aii) and (bii) are the histogram of particle size distribution.
Figure 1. SEM images of the as-prepared WO3 films and corresponding particle size distribution analysis through Nano Measure software; (a) 50 W; (b) 100 W, (ai) and (bi) are SEM images, where red line circles in (ai) and (bi) picture the particle size distribution, (aii) and (bii) are the histogram of particle size distribution.
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Figure 2. EC performances of the WO3 films prepared at the sputtering power of 50 W (a) and 100 W (b); response times (ai,bi), and memory effects (aii,bii) where the WO3 films were colored at 3 V for 5 min and then the transmittance spectra were recorded after different durations of 0 h, 4 h and 24 h.
Figure 2. EC performances of the WO3 films prepared at the sputtering power of 50 W (a) and 100 W (b); response times (ai,bi), and memory effects (aii,bii) where the WO3 films were colored at 3 V for 5 min and then the transmittance spectra were recorded after different durations of 0 h, 4 h and 24 h.
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Figure 3. Electrochemical performances of the WO3 films during 5000 cyclic voltammetry (CV) cycles prepared at the sputtering power of 50 W (a) and 100 W (b), the transmittance modulation rate at wavelength of 550 nm (ai,bi), charge density attenuation and evolution of Li ion accumulation (aii,bii), diffusion coefficients of Li ions (aiii,biii).
Figure 3. Electrochemical performances of the WO3 films during 5000 cyclic voltammetry (CV) cycles prepared at the sputtering power of 50 W (a) and 100 W (b), the transmittance modulation rate at wavelength of 550 nm (ai,bi), charge density attenuation and evolution of Li ion accumulation (aii,bii), diffusion coefficients of Li ions (aiii,biii).
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Figure 4. SEM morphology evolution of the WO3 films in bleached state during 5000 CV cycles prepared at the sputtering power of 50 W (a) and 100 W (b), after 3 cycles (ai,bi), after 1000 cycles (aii,bii), after 3000 cycles (aiii,biii), and after 5000 cycles (aiv,biv), where red line circles indicate the micro-cracks in the 50 W-deposited film and partly loose areas in the 100 W-deposited film.
Figure 4. SEM morphology evolution of the WO3 films in bleached state during 5000 CV cycles prepared at the sputtering power of 50 W (a) and 100 W (b), after 3 cycles (ai,bi), after 1000 cycles (aii,bii), after 3000 cycles (aiii,biii), and after 5000 cycles (aiv,biv), where red line circles indicate the micro-cracks in the 50 W-deposited film and partly loose areas in the 100 W-deposited film.
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Figure 5. AFM morphology evolution of the WO3 films during one-step Li ion insertion and extraction prepared at the sputtering power of 50 W (a) and 100 W (b), the original state (ai,bi), the colored state (aii,bii), and the bleached state (aiii,biii), where blue line circles indicate the cluster spikes.
Figure 5. AFM morphology evolution of the WO3 films during one-step Li ion insertion and extraction prepared at the sputtering power of 50 W (a) and 100 W (b), the original state (ai,bi), the colored state (aii,bii), and the bleached state (aiii,biii), where blue line circles indicate the cluster spikes.
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Figure 6. Failure analysis of the WO3 films with different granularity uniformity. Nonuniform state illustration of the 50 W-deposited WO3 film (ai) and uniform state illustration pf the 100 W-deposited WO3 film (bi), corresponding finite element simulation analysis (aii,bii), and cross-sectional SEM images of the WO3 films after 5000 CV cycles (aiii,biii), where red line circles indicate the cracks in the 50 W-deposited WO3 film.
Figure 6. Failure analysis of the WO3 films with different granularity uniformity. Nonuniform state illustration of the 50 W-deposited WO3 film (ai) and uniform state illustration pf the 100 W-deposited WO3 film (bi), corresponding finite element simulation analysis (aii,bii), and cross-sectional SEM images of the WO3 films after 5000 CV cycles (aiii,biii), where red line circles indicate the cracks in the 50 W-deposited WO3 film.
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MDPI and ACS Style

Zhang, Z.; Chen, H.; Lin, Z.; Guan, X.; Zhang, J.; Tang, X.; Zhan, Y.; Luo, J. Pivotal Role of the Granularity Uniformity of the WO3 Film Electrode upon the Cyclic Stability during Cation Insertion/Extraction. Nanomaterials 2023, 13, 973. https://doi.org/10.3390/nano13060973

AMA Style

Zhang Z, Chen H, Lin Z, Guan X, Zhang J, Tang X, Zhan Y, Luo J. Pivotal Role of the Granularity Uniformity of the WO3 Film Electrode upon the Cyclic Stability during Cation Insertion/Extraction. Nanomaterials. 2023; 13(6):973. https://doi.org/10.3390/nano13060973

Chicago/Turabian Style

Zhang, Zhaocheng, Haoyuan Chen, Zicong Lin, Xiongcong Guan, Jiong Zhang, Xiufeng Tang, Yunfeng Zhan, and Jianyi Luo. 2023. "Pivotal Role of the Granularity Uniformity of the WO3 Film Electrode upon the Cyclic Stability during Cation Insertion/Extraction" Nanomaterials 13, no. 6: 973. https://doi.org/10.3390/nano13060973

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